Template syntheses involving carbon acids. Synthesis and

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Znorg. Chem. 1986, 25, 4260-4261

4260

Contribution from the Institut de Chimie Mintrale et Analytique, Universite de Lausanne, Place du Chlteau 3, CH-1005 Lausanne, Switzerland, Department of Chemistry, Victoria University of Wellington, Wellington, New Zealand, Department of Chemistry, The University of Newcastle, Newcastle, New South Wales 2308, Australia, Research School of Chemistry, The Australian National University, Canberra, ACT 2601, Australia, and Department of Physical and Inorganic Chemistry, The University of Western Australia, Nedlands, WA 6009, Australia

Template Syntheses Involving Carbon Acids. Synthesis and Characterization of (3,10-Dimethy1-3,1O-dinitro1,4,8,11- tetraazacyclotetradecane)copper(11) and (1,9-Diamino-5-methyl-5-nitro-3,7-diazanonane)cop~r(II)Cations and Nitro Group Reduction Products Peter Comba,' Neil F. Curtis,*2 Geoffrey A. L a ~ r a n c e , *Alan ~ M. S a r g e ~ o nBrian , ~ W. S k e l t ~ n , ~ and Allan H. White*5 Received February 25, 1986 Reaction of C ~ ( e n ) (en ~ ~ =+ 1,2-diaminoethane)in methanol with formaldehydeand nitroethane in the presence of a noncoorand (1,9dinating base proceeds readily to produce (3,10-dimethyl-3,10-dinitro-1,4,8,1l-tetraazacyclotetradecane)copper(II) diamino-5-methyl-5-nitro-3,7-diazanonane)cop~r(II)cations as the only major products. These can be readily separated chromatographically or may be prepared separately via different optimized reactions. Reduction of the nitro groups of these complexed ligands may be achieved by zinc/acid or tin/acid reduction or catalytic hydrogenation;the former lead to some fragmentation of the precursor macrocyclic ligand during reduction, while the latter yields the amine cleanly. Copper(I1) complexes of the reduced and (5-ammoforms of the ligands, namely the (3,10-diammonio-3,10-dimethyl-1,4,8,1l-tetraazacyclotetradecane)copper(II) nio-l,9-diamino-5-methyl-3,7-diazanonane)copper(II) cations, have been characterized. With the macrocyclic ligands, rac and meso isomers have been identified, the meso form being the major product. Apart from the ligands described above, other products 1,3-diazacyclohexane)copper(II) cation, were undetected or negligible; only the aqua( 1,3-bis(2-aminoethy1)-5-ammonio-5-methylpresent in about 3% in the reduced ligand mixture, was present in sufficient amounts to permit characterization. Complexes were characterized by electronic, infrared, and electron spin resonance spectroscopy, and two were the subject of single-crystalX-ray perchlorate hexahydrate crystallographic analyses. (3,10-Diammonio-3,10-dimethyl-1,4,8,1l-tetraazacyclotetradecane)copper(II) crystallizes in the monoclinic space group P2,/c, a = 8.77 (2) A, b = 14.08 (1) A, c = 13.59 (2) A, and 0 = 107.5 (1)O, with the copper atom located at a crystallographic center of symmetry so that the molecular cation is also centrosymmetric with the CuN4 atoms coplanar. Copper-nitrogen distances are 2.021 (5) and 2.027 (6) A, while inversion-related perchloratesoccupy the fifth and sixth sites with Cu-0 = 2.523 (7) A. The minor species aqua( 1,3-bis(2-aminoethyl)-5-ammonio-5-methyl-1,3-diazacyclohexane)copper(II) perchlorate also crystallizes in the monoclinic space group P2,/c, a = 12.661 (3) A, b = 13.660 (7) A, c = 16.403 (4) A, and 0 = 130.03 (2)', with the copper ion in a pseudo-s uare planar coordination environment comprising the water molecule at 1.968 (5) A and three nitrogens at distances near 2.0 Two nitrogens of the ligand are uncoordinated, the other sites about the copper being approached by perchlorate oxygen atoms (Cu-0 = 2.637 (5) and 2.820 (4) A). The copper environment deviates considerably from planarity, with atoms up to 0.15 A from the CuN30 least-squares plane, while the six-membered ring in the ligand adopts a chair conformation with all substituentsexcept copper and one metal-bound amine being equatorial.

1.

Introduction Metal template syntheses of multidentate and macromonocyclic ligands have been established over the last two decades as offering high-yielding and selective routes to new ligands and their complexes. The various synthetic routes to potentially multidentate ligands have been extensively and several types of template effects about transition-metal ions have been identified. A template effect may arise from the stereochemistry imposed by metal ion coordination of some of the reactants, promoting a series of controlled steps; this is the coordination or kinetic template effect and characteristically provides routes to products not formed in the absence of the metal ion.12*13 In addition, the thermodynamic template effect refers to reactions that do proceed in the absence of the metal ion but those in which the metal ion promotes

formation of desired products by removing them from the equilibrium.6 Lastly, an equilibrium template effect has been identified, where aspects of both effects mentioned above combine; the distinctive feature of this is the formation of different products in the absence of the metal ion.13 While template reactions can be compartmentalized as above, it may be more instructive to look at the specific types of reactions which have been developed in that area to date. They are quite limited in number. One of the most common methods has involved reaction of a bifunctional aldehyde or ketone with a complexed multidentate amine, e.g. eq 1, or the similar reaction of a po-

Universite de Lausanne. Present address: Institut filr Anorganische Chemie, Universitht Basel, Spitalstrasse 5 1, CH-4056 Basel, Switzerland.

Victoria University of Wellington. The University of Newcastle. The Australian National University. The University of Western Australia. Curtis, N. F. Coord. Chem. Rev. 1968, 3, 3. Lindoy, L. F.; Busch, D. H. Prep. Inorg. React. 1971, 6, 1. Healy, M. d. S.; Rest, A. J. Adv. Inorg. Chem. Radiochem. 1978, 21, 1. Black, D. S.C.; Hartshorn, A. J. Coord. Chem. Reu. 1972, 9, 219. Christensen, J. J.; Eatough, D. J.; Izatt, R. M. Chem. Rev. 1974, 74, 351.

Busch, D. H. Helv. Chim. Acta 1967, 174. Melson, G. A., Ed. Coordination Chemistry of Macrocyclic Complexes; Plenum: New York, 1982. Blinn, E. L.; Busch, D. H. Inorg. Chem. 1968, 7, 820. Thompson, M. C.; Busch, D. H. J. Am. Chem. SOC.1962, 84, 1762; 1964,86, 213.

tentially multidentate aldehyde with a simple diamine.'^^ A range of macrocycles form from reaction of acetone or similar ketone with complexes of multidentate amines, e.g. eq 2. In these

reactions, an aldol-like reaction of a ketone molecule with an initially formed coordinated imine is apparently involved.6 With dithiolates, reaction with dibromoalkanes are possible, e.g. eq 3.13 Less extensively studied but notable reactions are the reaction of nickel(I1) dimethylglyoxime with diphenylborinic acid aminoethyl

0020-1669/86/1325-4260.$01.50/00 1986 American Chemical Society

Inorganic Chemistry, Vol. 25, No. 23, 1986 4261

Template Syntheses Involving Carbon Acids

were not elucidated. Where simple bis and tris diamine complexes are of high stability, as with copper(I1) or nickel(II), reactions

ester (DPBE)where an 0-B-0 linkage is introduced in the resultant macrocycle14 (eq 4) and the reaction of a coordinated (eq 5 ) . dihydrazine with f~rmaldehyde'~

DPBE

(4)

similar to those observed about inert metal ions might be feasible. For example, with the Cu(en)zz+ ion, nitroethane, and formaldehyde, the expected product is the macromonocycle 1 and other condensation products such as the intermediate multidentate 2 (eq 8). In this paper we report facile high-yielding syntheses of

n

1

I

H2N

I

NH2

H2

Inert metal amine complexes also undergo reactions with formaldehyde in basic solution. The Co(en)zgly2+ ion reacts to form the 3,lO-dioxocyclam macromonocycle, characterized by a crystal structure ana1ysis.l6 This strategy was recently extended to tris(diamine) complexes M(en)3"+ (M = Co(III), Rh(III), Ir(III), Pt(1V)) with formaldehyde and the carbon acid nitromethane.17-19 This reaction probably involves formation of an imine and subsequent attack by -CHINOz anionz0 (eq 6). This

process leads in a stepwise manner to complete capping of the open faces of the octahedron to form a macrobicyclic complex in a remarkably facile and stereospecific reaction, eq 7. Where the NO2

I

Y io2 intermediate imine is exceptionally stable, as occurs with chromium(II1) complexes, reaction as described in eq 6 and 7 does not proceed, however.21 Attempts to perform the macrobicyclization in eq 7 about labile metal ions have been largely unsuccessful in protic solvents; condensation reactions that do m r (14) Schrauzer, G. N. Chem. Ber. 1962,95, 1438. (15) Alwck, N. W.; Tasker, P.A. J . Chem. SOC.,Chem. Commun. 1972, 1239. (16) Herlt, A. J.; Sargeson, A. M.; Springborg, J.; Taylor, D.; Geue, R.; Snow, M. R. J . Chem. SOC.,Chem. Commun. 1976,285. (17) Geue, R. J.; Hambley, T. W.; Harrowfield, J. M.; Sargeson, A. M.; Snow, M. R. J . Am. Chem. SOC.1984, 106,5478. (18) Boucher, H. A.; Lawrance, G. A.; Lay, P. A.; Sargeson, A. M.; Bond, A. M.; Sangster, D. F.; Sullivan, J. C. J . Am. Chem. SOC.1983,105, 4652. (19) Harrowfield, J. MacB.; Herlt, A. J.; Lay, P.A.; Sargeson, A. M.; Bond, A. M.; Mulac, W. A.; Sullivan, J. C. J . Am. Chem. SOC.1983, 105, 5503. (20) Sargeson, A. M. Pure Appl. Chem. 1984,56, 1603. (21) Sargeson, A. M., unpublished results.

n

2

the products described in eq 8 and the corresponding amines from nitro group reduction, in addition to electrochemical and spectroscopic characterization and structural characterization of one major and a minor product of the nitro ligand reduction reactions as the copper(I1) complexes. Experimental Section Syntheses. All reactions employed usually AR grade chemicals and solvents as supplied. [Cu(en),](CIO,), was prepared by addition of excess diaminoethane to methanolic copper perchlorate, followed by cooling. Crude Condensation Reaction. A solution of C~(C10.,)~.6H,0 (7.4 g) or Cu(NO3),.3H2O (4.8 g) and 1,2-diaminoethane (2.4 g, 1:2 molar ratio) in methanol (200 mL) was stirred and treated with slightly more than 2 molar equiv of nitroethane (3.2 g) and 4 molar equiv of 37% aqueous formaldehyde (5 mL). Either triethanolamine or triethylamine was added as base (-2 mL). The mixture was stirred and heated at -55 'C for 2 h and then allowed to cool to room temperature while being stirred. Saturated aqueous NaC10, solution was added with stirring until precipitation had commenced. After cooling in an ice bath the crude purple product (9.2 g) was collected, washed with ethanol and ether, and air-dried. The product proved to be overwhelmingly a mixture of two complexes, macromonocyclic [Cu(dinemac)] (CIO,), (l-(CIO4),) and multidentate [ C ~ ( n e l i n ) ] ( C l O ~(2-(C104),) )~ which could be separated readily by chromatography (vide infra). The relative amounts of the two complexes varied from batch to batch, being somewhat dependent on the amounts of nitroethane and formaldehyde employed and also dependent on the choice of base. Subsequently, optimized syntheses of the two major products were developed. Since chromatographic separation proved to be facile, either a general synthesis combined with chromatographic separation or an optimized synthesis may be employed; both are described below. Chromatographic Separation of Condensation Reaction Products. Crude complex mixture (1.5 g) was dissolved in distilled water (2 L) and sorbed onto a column of SP Sephadex C-25 cation-exchange resin (25 cm X 3.5 cm). After being washed with water (-l/, L), the column was treated with 0.2 M NaCl solution, eluting only two well-separated bands. Band 1: (1,9-Diamino-5-methyl-5-nitro-3,7-diazanonane)copper(II) (2) Perchlorate, [Cu(neIin)](ClO,),. This purple band was collected and treated with saturated aqueous NaC104 solution until copious precipitation occurred. After cooling, the product was collected, washed with ethanol, and dried in vacuo (55%). Anal. Calcd for C8H2,Cl2CuNSOlo: C, 19.95, H, 4.39; N, 14.54. Found: C, 19.9; H, 4.3; N, 14.2. Electronic spectrum (water): X, 529 nm (c 62.4 M-' cm-I), 248 (655). Band 2: (3,10-Dimethyl-3,10-dinitro-1,4,8,1 l-tetraazacyclotetradecane)copper(II) Cation, [Cu(dinemac)12* (1). The purple band was collected and cooled, yielding an immediate precipitate of a chloride sesquihydrate salt. This was collected, washed with ethanol, and dried in vacuo (1 1%). Anal. Calcd for C12H29C12C~N605 5: C, 30.03; H, 6.09; N, 17.51. Found: C, 30.0; H, 5.9; N, 17.4. Electronic spectrum (water): A-, 513 nm (c 69.2), 254 (3650). Addition of saturated NaC10, solution and cooling the filtrate yielded a second precipitate as the perchlorate demihydrate salt. This was collected, washed with ethanol, and dried in vacuo (34%). Anal. Calcd for C12H27C12C~N6012s: C, 24.43; H, 4.61; N, 14.25. Found, C, 24.5; H, 4.5; N, 14.2. Electronic spectrum (water): ,X, 512 nm (c 69.8 M-l cm-'), 251 (3400). Optimized Synthesis of (1,9-Diamino-5-methyl-5-Ntro-3,7-diazanonane)copper(II) (2) Perchlorate, [Cu(nelin)](CIO,),. To a solution of [Cu(en),](CIO,), (11.5 g) in methanol (200 mL) was added nitroethane

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Comba et al.

(5 mL) and triethanolamine (5 mL). While the mixture was stirred 72.7 M-I cm-I); pH -5, ,A, 516 nm (c 69.6 M-I cm-') 249 (-8050); under reflux, a solution of aqueous 37% formaldehyde (5 mL) in methpH -10.5, A, 519 nm ( 6 88.5 M-I cm-I) 254 (7970). anol (15 mL) was added dropwise over -1 h. The solution was then Band 5: rac - (3,10-Diammonio-3,IO-dimethyl-1,4,8,1 l-tetraazacyclocooled in an ice bath and the product collected, washed with ethanol, and tetradecane)copper(II) (3b) Perchlorate Dihydrate, rac-[Cu(diamair-dried (1 1 g). It was recrystallized from hot water or from hot acemacH2)](CI04),.2H20. The minor isomer of the macrocyclic complex tonitrile/propan-2-01. Anal. Calcd for CsH23C12C~N5010: C, 19.95; H, was the final band and was collected and isolated exactly as described 4.39; N, 14.54; Cu, 13.2. Found: C, 20.1; H, 4.4; N, 14.5; Cu, 13.2. for the major isomer (15%). Anal, Calcd for C12H36C14C~N6018: C, 19.02; H, 4.66; N, 11.09; Cu, 8.39. Found: C, 19.5; H, 4.4; N, 11.2; Cu Optimized Synthesis of (3,10-DimethyI-3,IO-dinitro-1,4,8,1 l-tetraa8.2. Electronic spectrum (water): pH -1, A, 511 nm (c 76.2 M-' zncyclotetradecane)copper(II) (1) Perchlorate, [Cu(dinen~ac)](CIO~)~. To cm-I); pH -5, A,, 512 nm (c 70.4 M-' cm-I), 249 (7250); pH -10.5, a solution of [C~(en)~](C10,), (1 1.5 g) in methanol (200 mL) was added nitroethane (10 mL) and triethylamine (10 mL). While the mixture was ,A, 511 nm (c 85.9 M-I cm-I), 253 (8250). Tin/Acid Reduction of Nitro Complexes. Crude [Cu(dinemac)]stirred under reflux, 37% aqueous formaldehyde solution (1 5 mL) was (C104)2and [ C ~ ( n e l i n ) ] ( C I O mixture ~)~ (3 g) from the initial reaction added dropwise over 1 h. After cooling in an ice bath, the product was was treated exactly as described for the zinc/acid reduction, except collected, washed with ethanol, and air-dried (1 1 g). It was recrystallized granulated tin was employed. As for the former reaction, a fragmentafrom hot water acidified with HCIO, or from hot acetonitrile/propantion band (-20%) was observed in addition to complexed amine ana2-01. Anal. Calcd for C12H26C12CUN6012: C, 24.80; H, 4.51; N, 14.47. logues of the dinemac and nelin ligands, but the minor cyclohexane Found: C, 24.6; H, 4.5; N, 14.4. The complex may also be obtained as derivative detected previously was not observed in this albeit smaller scale a chloride dihydrate salt by dissolving the perchlorate salt in a minimum reaction. volume of boiling water and adding a few drops of concentrated HCI. Catalytic Reduction of Nitro Compounds. Either [Cu(dinemac)]The precipitate formed on cooling can be collected and recrystallized (C104)2or [Cu(neIin)](ClO,), (- 1.0 g) in water (-200 mL) was mixed from hot water/propan-2-01. Anal. Calcd for Cl2H&12CUN604: C, with 10% Pd-C catalyst (80%). On one occasion with each nitro complex was dissolved in -1 M HCI (250 mL) with warming to -50 'C. precursor the product complex was chromatographed on SP Sephadex Granulated zinc (ca. I O g) was added and the warm solution allowed to C-25 resin. It could be shown that the reduced amino analogues of the react until the color of the solution disappeared (-2 h). The mixture nitro precursors were the only products (>97%). Products were charwas filtered to remove solids, and then saturated NaOH solution was acterized by spectroscopic comparisons with authentic samples and by added with stirring until the pH was 10. The mixture was filtered to microanalysis (C, H, N). remove Zn(OH)*, the solid washed with a little warm dilute NaOH, the Physical Methods. Electronic spectra were recorded on an Hitachi pH then raised to -12, and the process repeated. The filtrate was treated with concentrated HCI to pH -9, and excess C U ( N O ~ ) ~ - ~ H ~ O220A spectrophotometer. Infrared spectra were recorded on a PerkinElmer 3-300 spectrometer as KBr discs. Electron spin resonance spectra (4 g) was added with vigorous stirring. The resultant deep blue solution were recorded on a Jeol JES-PE spectrometer fitted with an Oxford was adjusted to pH -4 and diluted to -20 L. This solution was sorbed instruments ESR9 helium flow cryostat and a Model DTC 2 temperature onto a column (25 cm X 3.5 cm) of SP Sephadex C-25 resin and then controller. Concentrations of the fluid or frozen solutions were in the eluted with NaCl solution (pH -4), initially of 0.15 M and finally of range 10-5-10-3 M, while powders were undiluted. Voltammetry in 0.25 M concentration. Apart from uncomplexed copper, a number of aqueous 0.1 M NaC10, was performed with a conventional three-elecbands were collected, in order: trode configuration and argon purge gas using either a BAS Model CV27 Band 1. This was a relatively fast-moving band, highly soluble and or an AMEL Model 473 electrochemical controller. Working electrodes rapidly decomposed by acid, which analyzed best for the initial reactant were an EG & G PAR 303 for hanging mercury drop (HMDE) or Cu(en)?+. This arises presumably from fragmentation during reduction dropping mercury (DME) and glassy carbon or platinum billets. and accounts for -20% of total complexed copper. Since there was no Crystallography. Crystal Data for meso -[Cu(diamma~H~)](ClO,)~. evidence for higher multidentates, further characterization was not 6 H 2 0 (3a-(CI04),.6H20;C12H&14CUN6022): M , = 829.9; monoclinic, pursued. Band 2: Aqua( 1,3-bis(2-~minoethyl)-5-ammonio-5-methyl-1,3-diaza- space group R 1 / c ; a = 8.77 (2) b = 14.08 (1) c = 13.59 (2) A, p = 107.5 (I)', U = 1600 (2) A3;D, = 1.72 (1) g 0,(Z= 2) = 1.72 g cm-'; cyclohexane)copper(II)(5) Perchlorate, [Cu(bad~H)(H,o)](ClO~)~. This F(OO0) = 862; p~~ = 10.9 cm-'; specimen 0.34 X 0.26 X 0.26 mm; A*,,,in minor blue band was collected and treated with saturated sodium per= 1.24, A*,,, = 1.31; 2e,,, = 500; N = 1936, N , = 1393; R = 0.054, chlorate solution. Upon standing, blue plates of the complex deposited R'= 0.061; T 295 K. and were collected by filtration, washed with ethanol, and dried (3%). Crystal Data for [Cu(badcH)(H20)](ClO,)9 ( 5 - ( c 1 0 4 ) 3 ; Anal. Calcd for C9H26C13C~NS013: c , 18.57; H, 4.50; N, 12.02; c u , C9H26C13C~N5012): M, = 582.2; monoclinic, space group P ~ , / c(d,,, 11.0. Found: C, 18.9; H, 4.4; N, 11.8; Cu, 10.9. Electronic spectrum No. 14); a = 12.661 (3), b = 13.660 (7), c = 16.403 (4) A, p = 130.03 (water): pH -1, rapid dissociation; pH -5, A, 620 nm (c 86.6 M-' (2)O, U = 2172 (1) A'; D, = 1.78 (1) g cm-3, D, (Z = 4) = 1.78 g ~ m - ~ ; cm-I), 252 (3730); pH -10.5, A, 608 nm (c 82.0 M-' cm-I), 252 F(O0O) = 1196; pMo= 14.1 cm-'; specimen 0.32 X 0.28 X 0.35 mm; (7700). Band 3: (1,9-Diemino-5-ammonio5-methyl-3,7-diaznnonane)copper- A*,,, = 1.37, A*,,, = 1.48. 2e,, = 500; N = 3516, N , = 2765; R = 0.041, R' = 0.046; T 295 K. (11) (4) Perchlorate Monohydrate, [C~(amlinH)](ClO~)~.H~0. This Structure Determination. Unique data sets were measured within the major purple band was collected and treated with saturated NaC10, specified 20,, limit on a Syntex P21 four-circle diffractometer in consolution. Rapid crystallization ensued, and the complex was collected, ventional 28/8 scan mode and with a monochromatic Mo Kcu radiation washed with ethanol, and air-dried. Addition of ethanol to the filtrate source. N independent reflections were obtained, No with I > 3u(Z) being and cooling produced a second crop, collected as before (31%). Anal. considered "observed" and used in the full-matrix least-squares refineCalcd for C8H26C13C~NS0,3: C , 16.85; H, 4.60; N, 12.28; CI, 18.65; Cu, ment after analytical absorption correction and solution of the structures 11.14. Found: C, 16.8;H,4.9;N,11.9;CI, 19.1;Cu,11.1. Electronic by the heavy-atom method. Anisotropic thermal parameters were refined spectrum (water): pH -1, rapid dissociation; pH -5, A,, 531 nm (c for the non-hydrogen atoms; ( x , y, z ) were ~ located and refined for all 56.9 M-l cm-'), 247 (875); pH 10.5, A, 538 nm (c 73.0 M-' cm-I), ligand H atoms, (Ulao)Hbeing estimated. Residuals quoted on 14 at 241 (6860). convergence are conventional R and R'. Neutral-complex scattering Band 4: meso - (3,lO-Diammonio-3,l O-dimethyl-I ,4,8,11- tetraazacyfactors were used;22computation used the X-RAY 76 program system23 clotetradecane)copper(II) ( 3 4 Perchlorate Dihydrate, meso-[Cu(diamimplemented on a Perkin-Elmer 3240 computer by S. R. Hall. Important The isomer of the macrocyclic complex ma~H~)](Cl0~)~.2H ~ Omajor . results are given in Figures 1 and 2 and Tables I-IV; non-hydrogen atom was collected as the first of two closely running purple bands. Addition labeling is shown in the figures. Interatomic (non-hydrogen) distances, of saturated NaCIO, solution and cooling precipitated the complex, which was collected, washed with ethanol, and air-dried. A second crop was collected following addition of ethanol to the filtrate and further cooling (22) Ibers, J. A,, Hamilton, W. C., Eds. International Table for X-ray and was collected as before (51%). Anal. Calcd for Cl2H3,CI4CuN6OIs: Crystallography; Kynoch: Birmingham, England, 1974; Vol. I V . C, 19.02; H , 4.66; N, 11.09; Cu, 8.39. Found: C, 19.0, H, 4.7; N, 10.9; (23) Stewart, J. M., Ed. The X-ray System-Version of March 1976; TechCu, 8.4. Single crystals (for X-ray analysis) as blue prisms formed as nical Report TR-446, Computer Science Center, University of Marythe hexahydrate. Electronic spectrum (water): pH 1, A, 513 nm (t land: College Park, MD, 1976.

-

-

-

-

-

-

Inorganic Chemistry, VoZ. 25, No. 23, 1986 4263

Template Syntheses Involving Carbon Acids Table I. Non-Hydrogen Atom Coordinates for [Cu(diammacHz)] (C104)4.6H20 atom

Y

X

0 0.1803 0.2743 0.1678 0.0701 0.2826 0.0633 -0.0670 -0.1704 -0.2813 0.2885 0.1654 0.3157 0.2470 0.4340 -0.3189 -0.2880 -0.2442 -0.2583 -0.4851

2

(8) (11) (10) (11) (8) (10) (7) (10) (10)

Cation 0 -0.0745 -0.0281 0.0067 -0.0717 0.0462 0.0926 0.0629 0.1449 0.1103

(3) (8) (8) (1 1) (9) (3) (10) (10) (11) (9)

Anion 0.1684 (1) 0.1458 (4) 0.0894 (4) 0.2482 (4) 0.1893 (5) 0.1506 (1) 0.0668 (4) 0.2281 (4) 0.1419 (5) 0.1681 (5)

(4) (5) (4) (5) (4) (4) (3) (4) (5)

Solvent Molecules 0.5131 (8) 0.3969 (4) 0.8999 (9) 0.5854 (4) 0.3243 (10) 0.3370 (5)

Table 11. Non-Hydrogen Atom Coordinates for [Cu(badcH)(OHz)] ( c l o d 3 atom' X Y 0.08702 15) 0.23648 14) 0.0576 ( 3 ) ' 0.2857 (3)' 0.1241 (3) 0.1919 (2) -0.0107 (5) 0.1574 (4) -0.1215 (5) 0.2266 (4) 0.2389 (3) -0.1120 (4) 0.2697 (3) 0.1844 (4) 0.3158 (3) 0.2997 (3) 0.3946 (4) 0.3564 (5) 0.4889 (4) 0.2809 (5) 0.5230 (3) 0.2984 (4) 0.2425 (3) 0.4056 (4) 0.1974 (3) 0.2829 (4) 0.1580 (3) 0.3462 (5) 0.0817 (4) 0.4571 (5) 0.1127 (3) 0.2263 (5) 0.0186 (1) 0.0563 (1) 0.0658 (3) 0.0158 (4) -0.0684 (3) -0.0219 (4) 0.0810 (3) 0.0190 (5) 0.0017 (5) 0.1968 (5) 0.0307 (1) 0.3098 (1) 0.0459 (3) 0.1753 (3) 0.0910 (3) 0.3202 (4) 0.0591 (4) 0.4113 (4) 0.3267 (5) -0.0675 (3) 0.6848 (1) 0.2926 (1) 0.8015 (7) 0.2276 (5) 0.6521 (13) 0.3445 (11) 0.7444 (10) 0.3630 (7) 0.5729 (15) 0.2587 (10) 0.6359 (11) 0.2300 (7) 0.5871 (19) 0.3177 (10) 0.7401 (12) 0.3719 (6) 0.7302 (26) 0.2279 (10)

0 0.0972 (3) 0.1943 (4) 0.2580 (4) 0.2891 ( 5 ) 0.3569 (4) 0.2086 (4) 0.1 147 (3) 0.0664 (5) -0.0366 (4) -0.0461 -0.0040 -0.1071 -0.1100 0.0337 0.3242 0.2753 0.2912 0.4335 0.2986

(1) (4) (4) (5) (5) (1) (5) (5) (5) (5)

d

d Figure 1. The cation meso-(3,10-diammonio-3,1O-dimethyl1,4,8,11tetraazacyclotetradeane)copper(II). 20% thermal ellipsoids are shown for the non-hydrogen atoms; hydrogen atoms have arbitrary radii of 0.1

A.

0.0583 (4) 0.0087 (4) 0.1822 (4)

Z

0.24145 14) 0.3383 (3)' 0.1453 (3) 0.0446 (4) 0.0169 (3) 0.1106 (3) 0.1235 (3) 0.2235 (3) 0.2010 (4) 0.1758 (4) 0.2696 (3) 0.2953 (4) 0.3597 (3) 0.3146 (4) 0.3883 (4) 0.2075 (3) 0.3614 (1) 0.2684 (3) 0.3316 (4) 0.4098 (4) 0.4322 (4) -0.0008 (1) -0.0313 (3) -0.0659 (3) 0.1078 (3) -0.0152 (4) 0.2103 (1) 0.2782 (6) 0.2572 (10) 0.1816 (10) 0.1231 (11) 0.2542 (8) 0.1148 (8) 0.2728 (7) 0.1829 (22)

OAtoms marked with an asterisk were refined with a population of 0.5. interatomic angles, ligand hydrogen geometries, structure factor amplitudes tables, thermal parameters and hydrogen atom parameters are deposited as supplementary material. Extinction was not a significant problem in either structure.

U

Figure 2. The cation aqua( 1,3-bis(2-aminoethyl)-5-ammonio-5methyl- 1,3-diazacyclohexane)copper(II). Table 111. Copper Atom Environments' [Cu(diammacH2)](C104)4.6H20 r N(5) N(1) N(5) 0(11)

r

N(l) N(5) N(12) 0 O(11) 0(12)b

2.007 (5) 2.002 (3) 2.000 (3) 1.968 ( 5 ) 2.637 (5) 2.820 (4)

2.021 ( 5 ) 2.027 (6) 2.523 (7)

94.3 (2)

0111) 95.4 (2) 87.9 (2)

[Cu(badcH)(OH~)l(ClO~)~ N(5) N(12) 0 O(11) 84.9 (2) 86.1 (2) 177.0 (2) 98.1 (2) 164.7 (2) 93.9 (2) 86.9 (1) 95.7 (2) 82.2 (1) 84.5 (2)

0(12)b 96.0 (2) 120.3 (1) 72.9 (1) 82.2 (2) 150.3 (2)

" r is the copper-ligand distance (A); other entries are the angles (deg) subtended by the relevant atoms of the head of the row and column. Independent geometries only are given. b(.t, + y . - 2). Table IV. Macrocyclic Torsion Angles (deg) for [Cu(diammacH2)](C104)4.6H20 (Atoms Denoted by Number; Nitrogen Atoms Italicized) atoms angle atoms angle -1.4 4-5-6-7 8.7 7-1-2-3 1-2-3-4 -109.5 5-6-7-1' -122.9 2-3-4-5 108.2 6-7-1 "2' 6.9 3-4-5-6 0.6

4264 Inorganic Chemistry, Vol. 25, No. 23, 1986

Comba et al. Table V. Ring Torsion Angles (deg) for [Cu(badcH)(OH,)](CIO,), (Atoms Denoted by Number; Nitrogen Atoms Italicized)

atoms 6-1-2-3 1-2-3-4 2-3-4-5

angle -65.4 59.3 -55.9

atoms -3-4-5-6 4-5-6-1 5-6-1-2

angle 56.6 -59.1 64.6

meso:rac forms were isolated in an approximately 3:l ratio, consistent with the result for the diammac macrocycle. Minor spectroscopic differences between the isolated forms support their assignment as the proposed and expected geometrical isomers. L 1 1800 lL00 loo0 cm” Assignment of the major diammac isomer as the meso form Figure 3. Infrared spectra of the meso (A) and roc (B) isomers of was confirmed by the crystallography. Single-crystal X-ray (3,10-diammonio-3,lO-dimethyl-l,4,8,11-tetraazacyclotetradecane)cop- structure determination establishes the structure of the perchlorate per(I1) as KBr disks (3a and 3b, respectively). with the disalt of 3a to be [C~(diammacH~)](C10~)~.6H~O, protonated diammac macrocycle in the meso configuration. Variations and Abnormal Features. For aqua( 1,3-bis(2-aminoLocation and meaningful refinement of hydrogen atom positional ethyl)-5-ammonio-5-methyl-1,3-diazacyclohexane)copper(II) (5) perparameters for the ligand suggests affiliations of 1, 3, and 1 chlorate, the third perchlorate ion is disordered over two locations; two hydrogens, respectively, with N ( l ) , N(31), and N(5), although sets of oxygen atoms were successfully refined with anisotropic thermal the hydrogen affilitation of the solvent molecule is crystalloparameters and populations constrained at 0.5 in the final model. For graphically undetermined. Half of the formula unit comprises meso-(3,10-diammonio-3,lO-dimethyl1,4,8,11-tetraazacyclotetradecane)copper(II) ( 3 4 perchlorate, measurement of data was hampered the asymmetric unit of the structure; the copper atom is located by wide line widths and decomposition (compensated for by scaling) in at a crystallographic center of symmetry, so that the cation is also the X-ray beam. Anion thermal motion is very high; V,, for C(6) was centrosymmetric. Copper-nitrogen distances are 2.021 (5) and not positive definite and was refined as the isotropic form. (This however, 2.027 (6) A, in a pseudo-square-planar disposition about the did not inhibit successful definition of the hydrogen atom disposition for copper. CuN, is necessarily planar because of the center of the ligand.) Solvent hydrogen coordinates were estimated from difference symmetry; other ligand atom deviations from this plane, S(C(2)), maps but would not refine meaningfully. 6(C(3)), 6(C(31)), 6(C(4)), 6(C(6)), 6(C(7)), and S(N(31)), are Results 0.79, 0.39, -1.08,0.83, 0.40, -0.35, and 1.23 A, respectively. The fifth and sixth coordination sites of the copper are ap roached Condensation about Cu(en),,+ in methanol with formaldehyde by inversion-related perchlorate O(11) at 2.523 (7) . Nonand the carbon acid nitroethane proceeds readily and is quite hydrogen atom coordinates, distances and angles in the copper specific, with the macromonocyclic tetraamine complex [Cuatom environment, and macrocyclic torsion angles are collected (dinemac)12+ (1) and the related multidentate [Cu(nelin)I2+(2) in Tables I, 111, and IV. An ORTEP drawing of the cation appears as the only major products. Sensitivity of the reaction to choice in Figure 1. The coordination geometry is very similar to that of noncoordinating base and relative amounts of reactants, preobserved for [ C ~ ( c y c l a m ) ] ( C 1 0 ~ also ) ~ , centrosymmetric with sumably related to the markedly different stabilities of the cyclic and Cu-N = 2.02 (4) and 2.02 (3) 8, and Cu-0 2.57 (4) and noncyclic products in acid, allowed optimized routes for the a hexamethyl derivative of cyclam which has Cu-N = 2.018 (4), synthesis and recrystallization of each product to be developed. 2.028 (4), 2.028 (4),and 2.045 (4) 8,and Cu-0 = 2.67 (4) and In common with copper(I1) complexes of most saturated ma2.70 (4) cromonocyclic tetraamines, the dinemac complex is stable for long Apart from the expected products Cu(nelin)2+ and Cu(dineperiods in quite strong acid, while the nelin complex is rapidly mac)2+, no other species were detected chromatographically, but dissociated. Analogous syntheses can be performed with nitrothey may have been present as minor components of the observed propane as the carbon acid. bands. Likewise, chromatographic separation on SP Sephadex Nitro group reduction proceeds cleanly by using hydrogen and C-25 resin of the copper(I1) complexes of the reduced (pendant Pd-C catalyst to generate the reduced amine form of the ligand. amine) ligands identified the expected Cu(diammac)2+ (3) and However, reduction with zinc or tin in acid occurs with some Cu(amlin)2+ (4) complexes (or their protonated forms) as the fragmentation of the precursor molecules, although it still offers major multidentate products. Only one other band was detected a facile and relatively high-yielding route. The pendant amines from a relatively large scale Zn/HCI reduction and was present on both the reduced macrocycle (diammac) and linear multito 43% only. Crystallization of this complex was achieved from dentate (amlin), although potentially able to coordinate to axial aqueous perchlorate solution, and microanalysis fitted a structure sites above and below the copper(I1)-tetraamine plane, show no incorporating the potentially five-coordinate ligand 1,3-bis(2evidence of doing so, since electronic and electron spin resonance aminoethyl)-5-amino-5-methyl1,3-diazacyclohexane (badc, V). spectroscopy in basic aqueous or aprotic solutions are not consistent A single-crystal X-ray structure determination established the with CuN6 chromophores, as described in the Discussion. structure of the perchlorate salt of 5 as [Cu(badcH)(OH,)]The dinemac macrocycle can in principle exist in either meso (CIOJ3, with the monoprotonated base badc described above (anti) or ruc (syn) form, depending on whether nitro groups are coordinated as a tridentate ligand, as shown in Figure 2. Location on opposite sides or the same side of the macrocyclic plane, reand meaningful refinement of all hydrogens atoms of the structure spectively; the same applies to the reduced diammac macrocycle. suggest affiliation of 2,0, 3, and 2 hydrogens, respectively, with With the copper(I1) diammac complex, chromatographic sepaN(12), N(3), N(32), and N(5) and a normal H2O water molecule. ration of the protonated pendant amine diastereoisomers was One formula unit comprises the asymmetric unit of the structure. achieved on Sephadex C-25 resin with the complexes being isolated Non-hydrogen atom coordinates, distances and angles in the copper in a meso:rac ratio of -3: 1. The two isomers show characteratom environments, and ring torsion angles are collected in Tables istically different electronic spectra and infrared spectra. In 11, 111, and V. aqueous base (pH 10.5) the electronic spectrum of the meso The copper atom in C ~ ( b a d c H ) ( 0 H , ) ~has + the common isomer has a maximum at 519 nm, but this is shifted to 51 1 nm pseudo-square-planar coordination environment comprised of the for the rac isomer; differences in acid are less marked but obvious water molecule (pyramidal at 0 with Cu-0-H(a,b) = 112 (6) (seeExperimental Section). The infrared spectrum of each isomer and 120 (5)O and H-O-H = 111 (7)O), N ( l), N ( 12), and N(5), is reproduced in part in Figure 3, and the differences are prothe distances to the latter all lying between 2.00 and 2.01 A. N(3) nounced. The spin resonance spectra also differ slightly. Although chromatographic separation of the Cu(dinemac) isomers was not achieved, preferential crystallization of the rac isomer from (24) Tasker, P. A.; Sklar, L. J . Cryst. Mol. Struct. 1975, 5, 239. chloride ion solution appears to have occurred and again assigned (25) Ochiai, E. I.; Rettig, S . J.; Trotter, J. Can. J . Chem. 1978, 56, 267. I

w

-

~~

Inorganic Chemistry, Vol. 25, No. 23, 1986 4265

Template Syntheses Involving Carbon Acids

Table VI. Redox Couples for Copper(I1) Amine Complexes in Aqueous 0.1 M NaC104 Solution" dc cyclic voltammetryb complexf Cu(Ia) Cu(Ib) Cu(I1) Cu(II1a) Cu(I1Ib) Cu(1V) Cu(V)(OH2)

pH -6 -6 -6 -1 -5 -10 -1 -5 10 -5 10 -5 10

EL12(CdiIi), V -0.68 -0.72 -0.61 -0.78 -0.7 1 -0.86 -0.71 -0.65 -0.84 -0.66 -0.69 -0.38 -0.50

-

-

E 1 / 2 ( N 0 2 NHOH), V -0.95 -0.96 -1.01

ElI2(Cui1IL),C V -0.7 1 -0.74 -0.59 -0.81 -0.73 -0.89 -0.76 -0.70 -0.87 -0.65 -0.68 -0.37 -0.49

AE, mV irrev irrev 77 irrev irrev irrevd irrev irrev irrev 105 60 70 59

ip/im

-

EP(NO2

0.95

NHOH), V -0.99 -1.00 -1.06

0.95 0.96 -1c

0.92

-

"Measured at DME or HMDE vs. Ag/Ag+ at ambient temperature; reference electrode calibrated as -0.12 V vs. saturated calomel electrode. Behavior at solid billet electrodes qualitatively similar. cEpreported for irreversible couples. dI1l-defined anodic wave 190 mV more positive than the cathodic wave. e Complicated by adsorption effects. fPerchlorate salts. Table VII. Electronic Transitions and Spin Hamiltonian Parameters for Copper(I1) Complexes of Pendant Amine Multidentates spin Hamiltonian paramsb electronic transition" complexC 8, cm-l (a, M-'cm-I) giw gll Aim A, g, 18 590 (73) 2.104 2.055 Cu(IV) 2.202 85 32 Cu(II1a) 19270 (88) 2.102 2.054 2.198 88 34 Cu(I1Ib) 19 570 (86) 2.099 2.053 2.191 88 31 2.121 2.064 2.235 71 18 CW)(OHz) 16450 (82) 'Measured in water at pH

-

All

200 205 210 186

10. A values in lo4 cm-I. cPerchlorate salts.

and N(32) (the latter coordinately saturated by hydrogen atoms anyway) are uncoordinated, the fifth and sixth sites of the copper being approached by O(11) (2.637 ( 5 ) A) and O(12) (X, + y , - z) (2.820 (4) A) of one of the perchlorate ions. The copper environment deviates considerably from planarity; for a leastsquares plane calculated through 0, N ( l ) , N(12), and N(5) (x2, 1919), atom deviations respectively are 0.10,0.12, -0.15, and -0.14 A with ~ ( C U=) 0.07 A (Le. away from O(11)). In the fivemembered chelate rings, b(C(11)) and b(C(12)) are -0.43 and 0.10 and 6(C(5)) and 6(C(6)) are -0.10 and -0.74 A; Le., both rings are envelopes with the deviant atom that which is attached to the common tetrahedral N ( l ) (C(11) and C(6)). The sixmembered ring N(1), C(2), N(3), C(4), C(5), C(6) is a chair, with torsion angles in the bonds successively from N ( l ) being -65.4, 59.3, -55.9, 56.6, and -59.6' and all substituents except C u and N(5) being equatorial. The incorporation of the carbon acid nitroethane into the nelin(I1) and dinemac (I) ligands is supported by microanalysis and indirectly by the crystal structure of the reduced diammac complex (3a). The six-membered chelate ring with nitro and methyl

-

Ia X =NO:, (meso-dinemac) IIIa X =NH2(meso-dlammac)

A

Ib

X = NO2 (ruc-dinemac)

I I l b X = NH2 ( r s c -diammac)

uHN

HpN

I 1 X = NO2 tnelin)

I V X = NH2 (amltn) V

(badc)

substituents has been characterized structurally in a related copper(I1) complex.26 Further, characteristic infrared bands (26) Comba, P.; Hambley, T. W.; Lawrance, G. A. Helv. Chim. Acta. 1985, 68, 2332.

-

assignable to the nitro group occur at -1555 cm-' (s, uas) and 1355 cm-l (m, us), while irreversible reduction of the nitro groups occurs in the voltammetry. All nitro-substituted complexes exhibit a one-electron Cu(II)/Cu(I) couple and a multielectron irreversible -NHOH by comparison with similar wave assigned to -NO2 studies of nitro ligands on cobalt(II1) comple~es.~'In the pendant amine complexes the nitro reduction wave is absent, and the Cu(II)/Cu(I) couple is shifted to a different potential. The ElI2 values for the complexes are collected in Table VI. The copper couple is at best quasi-reversible, and the copper(1) compounds are not stable on the coulometric time scale. Amine ligands I11 and IV, apart from the four nitrogens about the copper square plane, have the capacity to coordinate the pendant amine groups in axial sites when these are not protonated. At least in aqueous solution, there is no evidence for this from electronic spectroscopy since spectra in acidic, neutral, and basic solution are very similar. While the crystal structure of complexed IIIa is of the diprotonated ligand, a crystal structure of the copper(I1)-complexed neutral ligand prepared by another route shows -OC103occupying the axial sites and not - N H , groups.28 Evidently, there is a preference for four-coordination about copper(II), and this was also probed in solution by electron spin resonance and electronic spectroscopy. Spin Hamiltonian parameters calculated from the ESR spectra of the complexed pendant amine ligands are collected in Table VII. The g values are indicative of a d& ground state, while the A parameters support a square-planar CuN4 geometry in solution. Typical spectra are shown in Figure 4. Minor differences in the ESR spectra of complexed IIIa and IIIb support their assignment as geometric isomers. Solvent effects on the spectra are small or absent, and the complexes of I11 and IV are spectroscopically very similar to Cu(cyclam)*+ (cyclam = 1,4,8,1 l-tetraazacyclotetradecane),29supporting no appreciable axial interaction by the pendant amines. Electronic spectra (Table VII) also do not support a CuN6 geometry in solution. Detailed analysis of spectra is deferred to the Discussion.

-

(27) Bond, A. M.; Lawrance, G. A.; Lay, P. A.; Sargeson, A. M. Inorg. Chem. 1983, 22, 2010. (28) Lawrance, G. A.'; Skelton, B. W.; White, A. H.; Comba, P. Aust. J. Chem. 1986, 39, 1101. (29) Addison, A. W.; Sinn, K. Inorg. Chem. 1983, 22, 1225.

4266 Inorganic Chemistry, Vol. 25, No. 23, 1986

Comba et al.

VI

n

VI1

n

VI11

Figure 4. ESR spectra in dimethyl sulfoxide at 4 K of (A)(1,g-diammonio-5-methyl-5-nitro-3,7-diazanonane)cpper(II) and the (B) meso and ( C ) rac isomers of (3,10-diammonio-3,10-dimethyl-1,4,8,1 I-tetraazacyclotetradecane)copper(II) cations (4,3a, and 3b,respectively). The marker of the reference material dpph is shown at the top of the spectra.

Discussion

IX

in aprotic solvents may improve yields of macrobicycles from complexes such as Ni(en)2+,2' but our results indicate that at least in protic solvents diamines of Ni2+ and Cu2+generate multidentate or macromonocyclic ligands from reaction with formaldehyde and carbon acids. Observed condensations about C u ( e n ) p are remarkably clean, with the only significant reaction being the six-membered ring formation based on condensation of two formaldehyde molecules and one nitroethane molecule with two cis primary amine sites. The only other complexed ligand identified was V, present to more than 3%, the nitro precursor of which might arise where a single formaldehyde has bridged the internal cis amines of I1 to form a six-membered diazacyclohexane ring with two pendant ethyl amines, presumably by reaction between an intermediate amino1 and the adjacent deprotonated amine. Both types of condensation reaction occurring here have been observed about inert metal ion comple~es.'~-*~~~~ The ligands prepared following nitro group reduction have pendant amines that in principle can coordinate axially (X). Such

The facility of template syntheses involving formaldehyde and carbon acids clearly demonstrated about inert metal ions"-20 extends to reactions about the relatively labile copper(I1) ion. Further work in progress has established that reactions like those described here about copper(I1) also occur about ni~kel(II).~OThe d9 copper(I1) ion displays Jahn-Teller effects, which usually distort an octahedral structure at least tetrag~nally.~'Stepwise enthalpies of formation of M(en)2+and M(en)f+ are lower for ds nickel(I1) than for copper(II), but the order is markedly reversed for the tris complexes as a consequence of Jahn-Teller destabilization with C ~ ( e n ) ~ ~Consequently, +.~~ while macrobicyclization is inherently possible about Ni(en)?+, the preference with copper(I1) for squareplanar or elongated octahedral geometries will probably direct carbon acid syntheses toward tetradentate and macromonocyclic ligand formation. This propensity toward planar four-coordinate ligands about copper(I1) has been applied here to the preferential synthesis of such species. Even about nickel(II), however, there is apparently a preference for the formation of such products. Recently, reaction of formaldehyde and ammonia with Ni(en)32+has been shown to form but the macrobicycle 1,3,6,8,10,13,16,19-octaaza[6.6.6]eicosane, in very low yield (The major product of the reaction of formaldehyde and ammonia with Ni(en)32+ is the tripodal hexadentate complex VI, with some formation of square-planar complex VI1 rather than the hexadentate macrobicycle VI11.30333 The cavity in the 20-membered [6.6.6]macrobicycles VI11 and IX is clearly appropriate for many M(II), M(III), and M(1V) ions, since very stable complexes of IX with all of the first-row metal ions in one or more of these oxidation states have been prepared by insertion of the metal ion into the free macrobicyclic ligand isolated from the cobalt Possibly reaction

axial interaction may be precluded by protonation, as in the product 3a, analyzed by X-ray crystallography in this study. However, an independent structure of the unprotonated form of meso-diammac (3a), prepared by another route, shows that perchlorate oxygens occupy the axial sites in the solid state in preference to the pendant amines.28 Inspection of models reveals that approach of the amine in X would have to be fairly close for it to occupy a position directly above the metal ion; longer metal-amine bonds lead to a lateral displacement. Given the propensity of Cu(I1) for elongated axial bonding, it is perhaps not surprising that coordination of the pendant amines is not observed. However, with nickel(II), meso-diammac (IIIa) coordinates as a hexadentate ligand or as a tetradentate ligand, and when coordinated to cobalt(III), IIIa acts as a hexadentate; characterization of these complexes is being p ~ r s u e d . ~ ~ , ~ ~ The spin Hamiltonian parameters observed for the copper(I1) amine complexes indicate a d,2-,,2' ground state, and they are compatible with square-planar structure with little axial interTypically, CuN, chromophores exhibit gll values in

(30) Curtis, N.F.;Morgan, K. R.; Gainsford, G . J.; Siriwardena, S., unpublished results. (31) Reinen, D.Comments Inorg. Chem. 1983, 2, 227. (32) Rossotti, F. J. C. In Modern Coordination Chemistry; Lewis, J., Wilkins, R., Eds.; Interscience: London, 1960; Chapter l. (33) Suh, M. P.;Shin, W.; Kim, D.; Kim, S . Inorg. Chem. 1984.23, 618. (34) Comba, P.;Sargeson, A. M.; Engelhardt, L. M.; Harrowfield, J. MacB.; White, A. H.; Horn, E.; Snow, M. R. Inorg. Chem. 1985, 24, 2325.

(35) Comba, P.;Engelhardt, L. M.; Harrowfield, J. MacB.; Lawrance, G . A.; Martin, L. L.; Sargeson, A. M.; White, A. H. J. Chem. Soc., Chem. Commun. 1985, 174. (36) Creaser, I. I.; Gahan, L. R.; Harrowfield, J. MacB.; Lawrance, G. A.; Martin, L. L.; Sargeson, A. M., unpublished results. (37) Geue, R. J.; McCarthy, M. G.;Sargeson, A. M.; Skelton, B. W.; White, A. H. Inorg. Chem. 1985, 24, 1609. (38) Lawrance, G.A.; Hambley, T. W., unpublished results.

X

XI

Template Syntheses Involving Carbon Acids the range 2.17-2.23 and g, values around 2.05. However, we should realize that differences in g values are usually very subtle; they may be the result of such different effects as tetrahedral distortion of square-planar species and changes in covalency, and they may be irrelevant for quantitative analysis.41 The A parameters are usually much more indicative of the local geometry. Here, observed All 190 G and A , 20 G are quite consistent with a square-planar geometry. Solvent effects (in water, dimethyl sulfoxide, or pyridine) on the observed spectra were small or not observed, implying that any interactions in the axial positions are weak even in basic solution. It has been found in general that 14-membered tetraza macrocyclic rings are well suited for square-planar coordination of copper, developing strong in-plane interactions, a high-energy d-d transition, large Allvalues, and small gllvalues.42 The complexed 14-membered macrocycles 3a and 3b fit this pattern. While electronic spectroscopy is a t best a modest guide to structure, Hathaway has found a correlation between the energies of the d-d transitions of CuN, ( x = 4-6) species and their s t r ~ c t u r e . , ~ Complexes with tetragonal-octahedra1 CuN, chromophores have transitions in the region 15 500-18 500 cm-I, and those with square planar CuN4 chromophores have transitions in the region 18 000-20000 cm-'. The copper(I1) complex of IX has a defined CuN6 chromophore and transitions in the region of 15 000 cm-' but is nearly trigonal prismatic.36 Absorbance maxima for the copper(I1) complexes of IIIa, IIIb, and IV have maxima in solution above 18 500 cm-', which is consistent with the essentially CuN, environment implied by electron spin resonance studies. The crystal structure analysis of the Cu(I1) complex of IIIa indicated planarity of the copper and four nitrogen donors. This is likely to be the preferred arrangement with the four-coordinate ligands. Only in complexes such as XIz6 are deviations from planarity clearly observed. This is largely a consequence of the enforced planarity of the pyridine rings, which might have an influence on the disposition of the tetrahedral carbon atoms in the ligand and hence the donor set. Unlike the case of copper(II), copper( I) amine complexes are commonly tetrahedral, and comparative crystal structures with tetradentate ligands coordinated to copper in both oxidation states exist.44 The voltammetric reductions of the copper(I1) complexes, defined as one electron by wave height comparisons with known one-electron couples, fall clearly into two groups. The macrocyclic ligand complexes undergo irreversible reductions, while the open-chain tetraamine complexes exhibit quasi-reversible behavior. The distinction may relate to the greater ability of the open-chain tetraamines to change geometry and adopt a tetrahedral coordination about the copper(1) ion. Not only may the cavity in the 14-membered macrocycles be inappropriate for the larger copper(1) ion, but the ability of these ligands to distort to a tetrahedral geometry is probably reduced, so that the copper(1) ion may dissociate and disproportionate rapidly. The copper(I1) complex of V, which exhibits tetrahedral distortion from a perfect square plane in the solid state, also produces quasi-reversible behavior in the voltammetry, as does the already tetragonally distorted

-

-

(39) Hathaway, B. J. Coord. Chem. Rev.1970, 5, 1; 1970, 5, 143;Struct. Bonding (Berlin) 1984, 57, 55. (40) Schneider, W.; Baccini, P. Helv. Chim. Acta 1969, 52, 1955. (41) Deeth, R.J.; Gerloch, M. Inorg. Chem. 1984, 23, 3846. (42) Miyoshi, K.;Tanaka, H.; Kimura, E.; Tsuboyama, S.; Murata, S.; Shimizu, H.; Ishizu, K. Inorg. Chim.Acta 1983, 78, 23. (43) Hathaway, B. J. J . Chem. SOC.,Dalton Trans. 1972, 1196. (44) Brubaker, G. R.;Brown, J. M.; Yeo, M. K.; Kinsey, R. A,; Kutchan, T. M.; Mottel, E. A. Inorg. Chem. 1979, 18, 299.

Inorganic Chemistry, Vol. 25, No. 23, 1986 4261 complex XI.z6 With none of these saturated multidentate amine ligands is the lifetime of the copper(1) complex substantial. The redox potentials for compounds l a and l b and also for 3a and 3b are not equivalent. Since electron spin resonance spectra and infrared spectra also differ, the definition of these species as meso and rac isomers seems adequately established. To date, structural characterization of only the meso isomer has been achieved with any metal ion, so final confirmation of the racemic forms has not been forthcoming. Determined E l I zvalues for the copper(II)/coppe.r(I) couple in the CuN, complexes vary between about -0.6 and -0.8 V (vs. Ag/Ag+) in water; the variation is presumably largely a consequence of the different substituent groups -NOz, -NH3+ (in acid), or -NHz (in base). Inductive effects of such substituents are not identical and have been defined previously on cobalt(II1) macrobicyclic comple~es.~'*~~ The irreversible multielectron reduction -NHOH, 4e, neutral solution) in compounds 1 and 2 (-NOz occurs at a somewhat more negative potential (--150 mV) than the like reduction in cobalt(II1) macro bicycle^.^^ In the latter compounds the nitro group is attached to an apical carbon (XII)

-

H 3 C v N 0 2

XI1

XI11

remote from the metal center while in the present complexes the nitro group may in certain conformations experience a closer approach to the metal ion and interact more directly with dZz,d,,, and d,, orbitals (XIII). The copper complex of V, which exhibits a C u N 3 0chromophore in the solid state, is reduced at a potential -200 mV more positive than that observed for the CuN, complexes. The syntheses established here for reaction with Cu(en)?+ are being extended to allow investigation of the facility of these reactions with other multidentate amine precursor complexes and with other carbon acids apart-from nitroalkanes. Comparison of the outcome of such condensation reactions around various metal ions is also being probed. Evidently, at least around copper(II), facile routes to new multidentate and macromonocyclic ligands can be developed from template reactions of multidentate amines with formaldehyde and carbon acids. Acknowledgment. We gratefully acknowledge support of this work by grants from the Australian Research Grants Scheme and the New Zealand University Grants Research Committee. Registry No. m e ~ o - l - ( C l O ~1041 ) ~ , 98-51-8;r~c-l-(ClO~)~, 10426511-4;2-(C104)2, 104198-53-0; 3*6H20, 104198-56-3; 3b, 104319-22-4; 4, 104198-59-6; 5, 104198-62-1;en, 107-15-3;Cu(Ia)+, 104198-63-2; Cu(Ib)+, 104265-12-5; Cu(II)+, 104198-64-3; Cu(IIIa)+, 104198-65-4; Cu(IIIb)+, 104265-13-6;Cu(IV)+, 104198-66-5;Cu(V)(OH,)+, 104198-67-6;Cu(Ia)2+ (hydroxyamine derivative), 104198-68-7;Cu(Ib)2+(hydroxyamine derivative), 104265-14-7;CU(II)~+ (hydroxyamine derivative), 104198-69-8;[ C ~ ( e n ) ~ ] ( C 1 036407-48-4; ~)~, nitroethane, 79-24-3;formaldehyde, 50-00-0. Supplementary Material Available: Tables of interatomic (non-hydrogen) distances and angles, ligand hydrogen geometries, non-hydrogen atom thermal parameters, and hydrogen atom parameters (20 pages); tables of structure factor amplitudes (17 pages). Ordering information is given on any current masthead page.

(45) Lay, P.A. Doctoral Dissertation, Australian National University, 1981.